Journal Home > Volume 17 , Issue 3
Nano Research 2024, 17(3): 2145-2153 https://doi.org/10.1007/s12274-023-6024-0
Research Article | Open Access | Issue | Published: 25 September 2023

Fabrication of sub-20 nm MoS2 horizontal nanowire on silicon substrates by inclusion of precursors into polystyrene-b-polyethylene oxide nanopatterns: Detailed structural investigation

Show Author's Information Tandra Ghoshal( ),  Michael A. Morris( )
School of Chemistry, AMBER and CRANN, Trinity College Dublin, Dublin, Ireland, D02 AK60
Keywords:
MoS2, photoluminescence, nanowires, block copolymer, X-ray photoelectron spectroscopy (XPS), mapping, inclusion
Topics:
Layered semiconductorsNarrow band gap semiconductors
Cite this article:
Ghoshal T, Morris MA. Fabrication of sub-20 nm MoS2 horizontal nanowire on silicon substrates by inclusion of precursors into polystyrene-b-polyethylene oxide nanopatterns: Detailed structural investigation. Nano Research, 2024, 17(3): 2145-2153. https://doi.org/10.1007/s12274-023-6024-0
Download citation
EndNote(RIS)
BibTeX

485

Views

51

Downloads

Citations

0

Crossref

0

WoS

0

Scopus

0

CSCD

Abstract Full text Electronic supplementary material About this article

Herein, we demonstrate the fabrication of sub-20 nm MoS2 horizontal nanowire arrays on silicon substrates using a self-assembled block copolymer assisted in situ inclusion approach. Microphase separated long-range ordered polystyrene-b-polyethylene oxide (PS-b-PEO) block copolymer (BCP) line-space nanopatterns were achieved through thermo-solvent annealing. The patterns produced had long-range order and domain sizes > 1 μm. The BCP structures were lightly etched and modified by anhydrous ethanol to facilitate insertion of molybdenum precursor within the film maintaining the parent BCP arrangements. Horizontal ordered molybdenum oxide nanowire arrays were then fabricated by ultraviolet (UV)/ozone treatment at room temperature. The oxides were converted to sulphides by thermal evaporation at different temperatures in Ar/H2 environment. X-ray photoelectron spectroscopy revealed the composition and phases of the molybdenum oxide and sulphide nanowires. Elemental mapping was performed to investigate the interfaces between the oxide and sulphide nanowires with the substrate surface. The formation and stability of the sulphide nanowires were studied at different temperatures. The photoluminescence and Raman properties were studied at different formation temperatures to investigate defects and estimate the number of layers.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Fabrication of sub-20 nm MoS2 horizontal nanowire on silicon substrates by inclusion of precursors into polystyrene-b-polyethylene oxide nanopatterns: Detailed structural investigation

Show Author's information Tandra Ghoshal( ), Michael A. Morris( )
School of Chemistry, AMBER and CRANN, Trinity College Dublin, Dublin, Ireland, D02 AK60

Abstract

Herein, we demonstrate the fabrication of sub-20 nm MoS2 horizontal nanowire arrays on silicon substrates using a self-assembled block copolymer assisted in situ inclusion approach. Microphase separated long-range ordered polystyrene-b-polyethylene oxide (PS-b-PEO) block copolymer (BCP) line-space nanopatterns were achieved through thermo-solvent annealing. The patterns produced had long-range order and domain sizes > 1 μm. The BCP structures were lightly etched and modified by anhydrous ethanol to facilitate insertion of molybdenum precursor within the film maintaining the parent BCP arrangements. Horizontal ordered molybdenum oxide nanowire arrays were then fabricated by ultraviolet (UV)/ozone treatment at room temperature. The oxides were converted to sulphides by thermal evaporation at different temperatures in Ar/H2 environment. X-ray photoelectron spectroscopy revealed the composition and phases of the molybdenum oxide and sulphide nanowires. Elemental mapping was performed to investigate the interfaces between the oxide and sulphide nanowires with the substrate surface. The formation and stability of the sulphide nanowires were studied at different temperatures. The photoluminescence and Raman properties were studied at different formation temperatures to investigate defects and estimate the number of layers.

Keywords: MoS2, photoluminescence, nanowires, block copolymer, X-ray photoelectron spectroscopy (XPS), mapping, inclusion

References(45)

[1]

Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Katsnelson, M. I.; Grigorieva, I. V.; Dubonos, S. V.; Firsov, A. A. Two-dimensional gas of massless Dirac fermions in graphene. Nature 2005, 438, 197–200.
DOI Google Scholar
[2]

Zhang, Y. B.; Tan, Y. W.; Stormer, H. L.; Kim, P. Experimental observation of the quantum hall effect and Berry’s phase in graphene. Nature 2005, 438, 201–204.
DOI Google Scholar
[3]

Splendiani, A.; Sun, L.; Zhang, Y. B.; Li, T. S.; Kim, J.; Chim, C. Y.; Galli, G.; Wang, F. Emerging photoluminescence in monolayer MoS2. Nano Lett. 2010, 10, 1271–1275.
DOI Google Scholar
[4]

Lauritsen, J. V.; Kibsgaard, J.; Helveg, S.; Topsøe, H.; Clausen, B. S.; Lægsgaard, E.; Besenbacher, F. Size-dependent structure of MoS2 nanocrystals. Nat. Nanotechnol. 2007, 2, 53–58.
DOI Google Scholar
[5]

Remskar, M.; Mrzel, A.; Skraba, Z.; Jesih, A.; Ceh, M.; Demsar, J.; Stadelmann, P.; Levy, F.; Mihailovic, D. Self-assembly of subnanometer-diameter single-wall MoS2 nanotubes. Science 2001, 292, 479–481.
DOI Google Scholar
[6]

Kim, H. C.; Park, S. M.; Hinsberg, W. D. Block copolymer based nanostructures: Materials, processes, and applications to electronics. Chem. Rev. 2010, 110, 146–177.
DOI Google Scholar
[7]

Mao, J.; Zhang, B. C.; Shi, Y. H.; Wu, X. F.; He, Y. Y.; Wu, D.; Jie, J. S.; Lee, C. S.; Zhang, X. H. Conformal MoS2/silicon nanowire array heterojunction with enhanced light trapping and effective interface passivation for ultraweak infrared light detection. Adv. Funct. Mater. 2022, 32, 2108174.
DOI Google Scholar
[8]

Mallikarjuna, K.; Shinde, M. A.; Kim, H. Electrochromic smart windows using 2D-MoS2 nanostructures protected silver nanowire based flexible transparent electrodes. Mater. Sci. Semicond. Process. 2020, 117, 105176.
DOI Google Scholar
[9]

Xiao, Y.; Zou, G. S.; Huo, J. P.; Sun, T. M.; Feng, B.; Liu, L. Locally thinned, core–shell nanowire-integrated multi-gate MoS2 transistors for active control of extendable logic. ACS Appl. Mater. Interfaces 2023, 15, 1563–1573.
DOI Google Scholar
[10]

Dieterle, G.; Mestl, M. Raman spectroscopy of molybdenum oxides. Phys. Chem. Chem. Phys. 2002, 4, 822–826.
DOI Google Scholar
[11]

Windom, B. C.; Sawyer, W. G.; Hahn, D. W. A Raman spectroscopic study of MoS2 and MoO3: Applications to tribological systems. Tribol. Lett. 2011, 42, 301–310.
DOI Google Scholar
[12]

Zhang, Z. G.; Wang, X. X.; Zhang, J.; Yu, M.; Zhang, J. C.; Zhang, H. D.; Long, Y. Z. Recent advances in 1D micro- and nanoscale indium oxide structures. J. Alloys Compd. 2018, 752, 359–375.
DOI Google Scholar
[13]

Wang, D. W.; Sheriff, B. A.; McAlpine, M.; Heath, J. R. Development of ultra-high density silicon nanowire arrays for electronics applications. Nano Res. 2008, 1, 9–21.
DOI Google Scholar
[14]

Cheng, J. Y.; Sanders, D. P.; Truong, H. D.; Harrer, S.; Friz, A.; Holmes, S.; Colburn, M.; Hinsberg, W. D. Simple and versatile methods to integrate directed self-assembly with optical lithography using a polarity-switched photoresist. ACS Nano 2010, 4, 4815–4823.
DOI Google Scholar
[15]
Bates, C. M.; Bates, F. S. 50th anniversary perspective: Block polymers-pure potential. Macromolecules 2017, 50, 3–22.
DOI
[16]

Gadelrab, K. R.; Hannon, A. F.; Ross, C. A.; Alexander-Katz, A. Inverting the design path for self-assembled block copolymers. Mol. Syst. Des. Eng. 2017, 2, 539–548.
DOI Google Scholar
[17]

Herr, D. J. C. Directed block copolymer self-assembly for nanoelectronics fabrication. J. Mater. Res. 2011, 26, 122–139.
DOI Google Scholar
[18]

Park, C.; Yoon, J.; Thomas, E. L. Enabling nanotechnology with self assembled block copolymer patterns. Polymer 2003, 44, 6725–6760.
DOI Google Scholar
[19]

Ghoshal, T.; Senthamaraikannan, R.; Shaw, M. T.; Holmes, J. D.; Morris, M. A. “In situ” hard mask materials: A new methodology for creation of vertical silicon nanopillar and nanowire arrays. Nanoscale 2012, 4, 7743–7750.
DOI Google Scholar
[20]

Ghoshal, T.; Shaw, M. T.; Holmes, J. D.; Morris, M. A. Development of a facile block copolymer method for creating hard mask patterns integrated into semiconductor manufacturing. Nano Res. 2016, 9, 3116–3128.
DOI Google Scholar
[21]

Rasappa, S.; Borah, D.; Faulkner, C. C.; Lutz, T.; Shaw, M. T.; Holmes, J. D.; Morris, M. A. Fabrication of a sub-10 nm silicon nanowire based ethanol sensor using block copolymer lithography. Nanotechnology 2013, 24, 065503.
DOI Google Scholar
[22]

Chaudhari, A.; Ghoshal, T.; Shaw, M. T.; O’Connell, J.; Kelly, R. A.; Glynn, C.; O’Dwyer, C. Holmes, J. D.; Morris, M. A. Fabrication of MoS2 nanowire arrays and layered structures via the self-assembly of block copolymers. Adv. Mater. Interfaces 2016, 3, 1500596.
DOI Google Scholar
[23]

Mokarian-Tabari, P.; Collins, T. W.; Holmes, J. D.; Morris, M. A. Cyclical ‘flipping’ of morphology in block copolymer thin films. ACS Nano 2011, 5, 4617–4623.
DOI Google Scholar
[24]

Ghoshal, T.; Chaudhari, A.; Cummins, C.; Shaw, M. T.; Holmes, J. D.; Morris, M. A. Morphological evolution of lamellar forming polystyrene-block-poly(4-vinylpyridine) copolymers under solvent annealing. Soft Matter 2016, 12, 5429–5437.
DOI Google Scholar
[25]

Mishra, V.; Fredrickson, G. H.; Kramer, E. J. Effect of film thickness and domain spacing on defect densities in directed self-assembly of cylindrical morphology block copolymers. ACS Nano 2012, 6, 2629–2641.
DOI Google Scholar
[26]

Zhang, X. H.; Berry, B. C.; Yager, K. G.; Kim, S.; Jones, R. L.; Satija, S.; Pickel, D. L.; Douglas, J. F.; Karim, A. Surface morphology diagram for cylinder-forming block copolymer thin films. ACS Nano 2008, 2, 2331–2341.
DOI Google Scholar
[27]

Ghoshal, T.; Senthamaraikannan, R.; Shaw, M. T.; Holmes, J. D.; Morris, M. A. Fabrication of ordered, large scale, horizontally-aligned Si nanowire arrays based on an in situ hard mask block copolymer approach. Adv. Mater. 2014, 26, 1207–1216.
DOI Google Scholar
[28]

Ghoshal, T.; Shaw, M. T.; Bolger, C. T.; Holmes, J. D.; Morris, M. A. A general method for controlled nanopatterning of oxide dots: A microphase separated block copolymer platform. J. Mater. Chem. 2012, 22, 12083–12089.
DOI Google Scholar
[29]

Ghoshal, T.; Maity, T.; Senthamaraikannan, R.; Shaw, M. T.; Carolan, P.; Holmes, J. D.; Roy, S.; Morris, M. A. Size and space controlled hexagonal arrays of superparamagnetic iron oxide nanodots: Magnetic studies and application. Sci. Rep. 2013, 3, 2772.
DOI Google Scholar
[30]

Ghoshal, T.; Maity, T.; Godsell, J. F.; Roy, S.; Morris, M. A. Large scale monodisperse hexagonal arrays of superparamagnetic iron oxides nanodots: A facile block copolymer inclusion method. Adv. Mater. 2012, 24, 2390–2397.
DOI Google Scholar
[31]

Giraud, E. C.; Mokarian-Tabari, P.; Toolan, D. T. W.; Arnold, T.; Smith, A. J.; Howse, J. R.; Topham, P. D.; Morris, M. A. Highly ordered titanium dioxide nanostructures via a simple one-step vapor-inclusion method in block copolymer films. ACS Appl. Nano Mater. 2018, 1, 3426–3434.
DOI Google Scholar
[32]

Ghoshal, T.; Ntaras, C.; Shaw, M. T.; Holmes, J. D.; Avgeropoulos, A.; Morris, M. A. A vertical lamellae arrangement of sub-16 nm pitch (domain spacing) in a microphase separated PS-b-PEO thin film by salt addition. J. Mater. Chem. C 2015, 3, 7216–7227.
DOI Google Scholar
[33]

Choi, J. G.; Thompson, L. T. XPS study of as-prepared and reduced molybdenum oxides. Appl. Surf. Sci. 1996, 93, 143–149.
DOI Google Scholar
[34]

Ho, S. F.; Contarini, S.; Rabalais, J. W. Metallization channels in ion-induced decomposition of molybdates and niobates. Chem. Phys. Lett. 1987, 133, 171–175.
DOI Google Scholar
[35]

Fleisch, T. H.; Mains, G. J. An XPS study of the UV reduction and photochromism of MoO3 and WO3. J. Chem. Phys. 1982, 76, 780–786.
DOI Google Scholar
[36]

Vernickaitė, E.; Lelis, M.; Tsyntsaru, N.; Pakštas, V.; Cesiulis, H. XPS studies on the Mo oxide-based coatings electrodeposited from highly saturated acetate bath. Chemija 2020, 31, 203–209.
DOI Google Scholar
[37]

Syari’Ati, A.; Kumar, S.; Zahid, A.; Ali El Yumin, A.; Ye, J. T.; Rudolf, P. Photoemission spectroscopy study of structural defects in molybdenum disulfide (MoS2) grown by chemical vapor deposition (CVD). Chem. Commun. 2019, 55, 10384–10387.
DOI Google Scholar
[38]

Lee, Y.; Lee, J.; Bark, H.; Oh, I. K.; Ryu, G. H.; Lee, Z.; Kim, H.; Cho, J. H.; Ahn, J. H.; Lee, C. Synthesis of wafer-scale uniform molybdenum disulfide films with control over the layer number using a gas phase sulfur precursor. Nanoscale 2014, 6, 2821–2826.
DOI Google Scholar
[39]

Li, B.; Jiang, L.; Li, X.; Ran, P.; Zuo, P.; Wang, A. D.; Qu, L. T.; Zhao, Y.; Cheng, Z. H.; Lu, Y. F. Preparation of monolayer MoS2 quantum dots using temporally shaped femtosecond laser ablation of bulk MoS2 targets in water. Sci. Rep. 2017, 7, 11182.
DOI Google Scholar
[40]

Tongay, S.; Suh, J.; Ataca, C.; Fan, W.; Luce, A.; Kang, J. S.; Liu, J.; Ko, C.; Raghunathanan, R.; Zhou, J. et al. Defects activated photoluminescence in two-dimensional semiconductors: Interplay between bound, charged and free excitons. Sci. Rep. 2013, 3, 2657.
DOI Google Scholar
[41]

Sam, R. T.; Umakoshi, T.; Verma, P. Probing stacking configurations in a few layered MoS2 by low frequency Raman spectroscopy. Sci. Rep. 2020, 10, 21227.
DOI Google Scholar
[42]

Cortijo-Campos, S.; Prieto, C.; De Andrés, A. Size effects in single- and few-layer MoS2 nanoflakes: Impact on Raman phonons and photoluminescence. Nanomaterials 2022, 12, 1330.
DOI Google Scholar
[43]

Buscema, M.; Steele, G. A.; Van Der Zant, H. S. J.; Castellanos-Gomez, A. The effect of the substrate on the Raman and photoluminescence emission of single-layer MoS2. Nano Res. 2014, 7, 561–571.
DOI Google Scholar
[44]

Mignuzzi, S.; Pollard, A. J.; Bonini, N.; Brennan, B.; Gilmore, I. S.; Pimenta, M. A.; Richards, D.; Roy, D. Effect of disorder on Raman scattering of single-layer MoS2. Phys. Rev. B 2015, 91, 195411.
DOI Google Scholar
[45]

Carvalho, B. R.; Wang, Y. X.; Mignuzzi, S.; Roy, D.; Terrones, M.; Fantini, C.; Crespi, V. H.; Malard, L. M.; Pimenta, M. A. Intervalley scattering by acoustic phonons in two-dimensional MoS2 revealed by double-resonance Raman spectroscopy. Nat. Commun. 2017, 8, 14670.
DOI Google Scholar
File
12274_2023_6024_MOESM1_ESM.pdf (281.2 KB)
Publication history
Copyright
Acknowledgements
Rights and permissions

Publication history

Received: 28 February 2021
Revised: 22 March 2021
Accepted: 07 April 2021
Published: 25 September 2023
Issue date: March 2024

Copyright

© The author(s) 2023

Acknowledgements

Acknowledgements

We acknowledge financial support from the Science Foundation Ireland AMBER grant 12/RC/2278. We would also like to thank Dr. Clive Downing for the TEM assistance.

Rights and permissions

Copyright: © 2021 by the author(s). This article is an open access article distributed under Creative Commons Attribution License (CC BY 4.0), visit https://creativecommons.org/licenses/by/4.0/.

Return